WO1997039890A1 - Multi-layer polymeric structure - Google Patents
Multi-layer polymeric structure Download PDFInfo
- Publication number
- WO1997039890A1 WO1997039890A1 PCT/US1997/007290 US9707290W WO9739890A1 WO 1997039890 A1 WO1997039890 A1 WO 1997039890A1 US 9707290 W US9707290 W US 9707290W WO 9739890 A1 WO9739890 A1 WO 9739890A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- polymer
- layers
- polymeric structure
- layer polymeric
- Prior art date
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- 229920000642 polymer Polymers 0.000 claims abstract description 58
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 33
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims abstract description 25
- 229920009441 perflouroethylene propylene Polymers 0.000 claims abstract description 25
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 20
- 239000004811 fluoropolymer Substances 0.000 claims abstract description 18
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001125 extrusion Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- -1 fluoroethylene, fluoropropylene Chemical group 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 93
- 239000000178 monomer Substances 0.000 description 22
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 9
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000003682 fluorination reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 3
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229960000834 vinyl ether Drugs 0.000 description 2
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002355 dual-layer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical group C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N vinyl ethyl ether Natural products CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/19—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their edges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/12—Articles with an irregular circumference when viewed in cross-section, e.g. window profiles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/02—Temperature
- B32B2309/025—Temperature vs time profiles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/12—Pressure
- B32B2309/125—Pressure vs time profiles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2597/00—Tubular articles, e.g. hoses, pipes
Definitions
- the invention relates to a multi-layer polymeric structure, to an apparatus comprising such a structure and to a process for manufacturing such a structure.
- multi-layer polymeric structures comprising at least three layers i.e. two dissimilar polymeric layers forming the outer surfaces of a structure bonded together by an adhesive tie- layer.
- the adhesive layer although in many cases thinner than the surface layers, alters the properties of the structure, generally requires a complicated manufacturing process for the structure and increases the cost thereof. For many applications it would be useful if relatively simple multi-layer structures which do not require an adhesive tie-layer, would be available for applications in which one surface of the structure could be subjected to significantly different conditions, compared with the other surface of the structure.
- a problem that arises in developing such desired structures is that significantly different conditions at two sides of the structure require, in general, chemically significantly different polymers to provide satisfactory performance under these conditions. And these chemically different polymers, when employed in layers, are not likely to adhere to each other in a sufficient manner to obtain a strong multi-layer structure without the use of one or more adhesive tie-layers between the desired polymer layers. Even in cases where compounds are miscible, they do not necessarily have adhesive properties for each other which would render them suitable for a multi-layer structure without adhesive layer
- Fluoropolymers are generally materials showing a good chemical resistance and temperature stability and have been applied in many forms, e.g. as tubes, sheets and shaped objects.
- fluorinated ethylene propylene polymers show excellent performance in chemically aggressive environments at elevated temperature and/or pressure.
- chemically- and/or thermally resistant perfluoroalkoxy polymers are required to withstand the environment to which one surface of a polymer structure is exposed. In that case the entire polymer structure had to be manufactured from the, generally more expensive, perfluoroalkoxy polymer material.
- the present invention it has become possible to tailor the polymeric material used in two sides of a structure to the different chemical-, physical- and/or mechanical requirements for each side without using an adhesive tie-layer. This means that chemically aggressive compounds permeating to a certain extent through a layer at one side cannot attack or dissolve a tie-layer. Moreover, in many cases the directly bonded polymer layers have an adhesive strength to one another which is in order of the cohesive strength of the component layers of the laminate as shown in some of the Examples hereinafter.
- both the perfluoroalkoxy polymer and the fluorinated ethylene propylene polymer employed in the polymeric structure comprise tetrafluoroethylene as monomer which selection of common monomer increases the compatibility of the two adjacent layers described hereinbefore. Moreover the selection of similar co-monomers in both polymers increases the compatibility even further.
- the fluorinated ethylene propylene polymer present in the polymer structure may be prepared by using two or more monomers. In case 0 two co-monomers are used, these are preferably perfluoro(alkyl vinyl ether), e.g., perfluoropropylvinylether, and hexafluoropropylene.
- the polymer can have a wide range of hexafluoropropylene content as disclosed in the literature, and in addition to the tetrafluoroethylene, can optionally contain one or more additional fluorine- containing co-monomers.
- a preferred additional co-monomer is fluoroalkylvinylether.
- the weight percentage of hexafluoropropylene co-monomer is from 7-30%, in particular 7-15% by weight of the total amount of the different co-monomers. Typical compositions of such polymers are described in International Standard No. ISO 12086- 1 : 1995(E).
- the fluorinated ethylene propylene polymer is a copolymer based on the co- monomers fluoroethylene, fluoropropylene and a perfluoroalkylvinylether; notably a perfluoromethylvinylether, perfluoroethylvinylether or perfluoropropylvinylether.
- the monomers fluoroethylene and fluoropropylene are preferably tetrafluoroethylene and hexafluoropropylene, respectively.
- An advantage of the application of a copolymer in a multi-layer polymeric structure according to the invention is the excellent compatibility between a layer comprising such a copolymer and at least one adjacent layer comprising a perfluoroalkoxy polymer.
- the alkyl-group present in the fluoroalkylvinylether comonomer may comprise 1-10 carbon atoms, and preferably 2-6 carbon atoms.
- the alkyl-group is a propyl-group
- the vinylether is perfluoropropylvinylether.
- such a copolymer comprises 7-30% by weight of hexafluoropropylene monomer, 92.9-60% by weight of tetrafluoroethylene monomer and 0.1-10% by weight of fluoroalkylvinylether, to total 100 wt%.
- such a copolymer is comprises 7-15% by weight of hexafluoropropylene monomer, 92.5-83% by weight of the tetrafluoroethylene monomer and 0.5-2% by weight of perfluoropropyl-or- ethylvinylether.
- the perfluoroalkoxy polymer present in the polymer structure may also be prepared by using additional co-monomer along with the fluoroethylene monomer.
- these are preferably hexafluoropropylene and a perfluoroalkylvinylether along with the fluoroethylene.
- the perfluoroalkoxy polymer contains 99.9-90% by weight of tetrafluoroethylene monomer and 0.1-10% by weight of a perfluoroalkylvinylether co-monomer. Even more preferably, the weight of percentage of tetrafluoroethylene is from 99.5-95% and for the perfluoroalkylvinylether from 0.5-5% by weight.
- the alkyl-group present in the perfluoroalkylvinylether may comprise 1-10 carbon atoms, and preferably 2-6 carbon atoms.
- the alkyl-group is selected from the series, consisting of methyl-, ethyl- and propyl- groups.
- layers in the multi-layer polymeric structure according to the present invention of which at least one individual layer comprises more than one fluoropolymer in the form of a blend or a melt compound, preferably of fluoropolymers present in at least two adjacent layers of the structure.
- At least one of the layers comprises a fluoropolymer of which a major fraction consists of a perfluoroalkoxy polymer and a minor fraction consists of a fluorinated ethylene propylene polymer.
- a major fraction consists of a perfluoroalkoxy polymer
- a minor fraction consists of a fluorinated ethylene propylene polymer.
- the major fraction amounts to 60-99% by weight and the minor fraction 1 -40% by weight, based on total polymer weight in that particular layer.
- At least one other adjacent layer comprises a fluoropolymer of which a major fraction consists of a fluorinated ethylene propylene polymer and a minor fraction consists of a perfluoroalkoxy polymer.
- the major fraction amounts to 60-99% by weight and the minor fraction 1-40% by weight, based on total polymer weight in that particular layer.
- the filler may comprise organic and/or inorganic material and preferably comprises carbon, glass in the form of particles or fibers or silicates. Such filler may be present in an amount of 0.1-50% by weight, and preferably of 0.2-20% by weight, based on the total weight of a single layer.
- filler material in a polymer layer has the further advantage of improving the surface smoothness of the layer, in particular if a polytetrafluoroethylene micropowder is used as filler material.
- a polytetrafluoroethylene micropowder is used as filler material.
- the largest dimension of one particle is from 0.1-50 ⁇ m, preferably from 0.5-10 ⁇ m.
- At least one of the polymer layers comprising a high purity perfluoroalkoxy polymer is particularly inert for certain chemicals; in that case it is envisaged to include at least one layer in the structure which comprises a post-fluorinated polymer.
- at least the layer comprising a perfluoroalkoxy polymer has been subjected to a post-polymerization fluorination treatment; the intensity of such a treatment is defined by a low level of extractable fluorine ions in the polymer layer after the treatment.
- the resulting high-purity perfluoroalkoxy polymer contains relatively low quantities of alkoxyfluoride-, carboxylic-, and vinyl- end groups.
- the use of a post-polymerization fluorination treatment for at least one polymer layer is combined with the use of inert filler material in that same layer in order to attain particularly inert and smooth surfaces. This is desirable for applications in the micro electronics industry, such as silicon-wafer manufacturing, and other applications such as for chemical transfer tubes and in medical-, pharmaceutical- and food processing applications.
- the multi-layer polymeric structures according to the invention can have many shapes such as flat sheets, profiled sheets, tubes and blow molding articles with a more complex form.
- the multi-layer structure in particular for use in heat-exchangers, has a tubular shape; the perfluoroalkoxy polymer (“PFA”) layer can be located either at the inside or the outside of the tube depending on the application and taking into account that for most applications the PFA is able to withstand more severe conditions than the FEP.
- PFA perfluoroalkoxy polymer
- the PFA layer will have its outer surface in contact with the flue gas, whereas the FEP layer will have its outer surface in contact with the "clean" fluid.
- the multi-layer structures according to the present invention include structures having more than two layers of polymer, depending on the application.
- a preferred embodiment of the invention relates to three-layer structures comprising a FEP polymer layer of which both surfaces are covered by PFA layers.
- PFA layers For certain applications, such as in the semi-conductor industry, it may be advantageous to subject the outer surfaces of the two PFA layers to a post-polymerization fluorination treatment as described hereinbefore.
- a first PFA layer is employed as central layer, one surface thereof being adjacent to an FEP layer and the other surface being adjacent to a second PFA layer which optionally may be subjected to a post-polymerization fluorination treatment.
- a three layer polymer structure is eminently suitable for applications in the semi-conductor industry and other sectors where very high requirements are in force for the chemical- and mechanical stability of the structures.
- the invention further relates to a process for manufacturing a multi-layer polymeric structure as described hereinbefore in which the fluoropolymers for at least two adjacent layers are co-extruded.
- at least two different extruders feed one common extrusion head in which the individual layers of fluoropolymers are coextruded to flow together for a period of 0.1-50 s at a pressure of 2-300 bar and a temperature of 50°-400°C, in order to allow reptation between the different US97/07290 fluoropolymer layers, resulting in excellent adhesion between the different layers.
- the fluoropolymers are preferably extruded at a melt flow rate of 0.8-40 g/10 min., in particular of 0.8-25 g/10 min., according to ASTM D 2116 (for FEP) and ASTM D 3307 (for PFA).
- multi-layer polymeric structures according to the invention can be advantageously applied in the semi-conductor manufacturing industry, as chemical liners for vessels, in the food processing industry and in general for self-cleaning types of equipment.
- Fluorinated ethylene propylene polymer comprising 87% by weight of monomer tetrafluoroethylene and 13% by weight of co ⁇ monomer hexafluoropropylene and having a melt flow rate of 2.7 g/10 min (4.67 . IO -6 kg/s) according to ASTM D-2116 was introduced into a first single-screw extruder having a diameter of 45 mm (4.5 . 10 ⁇ 2 m) and a length/diameter ratio of 24, operating at the following conditions: 320°-370°C, 0.75 .
- FEP Fluorinated ethylene propylene polymer
- the outer layer of this structure consisted of perfluoroalkoxy (PFA) polymer, comprising 96% of monomer tetrafluoroethylene and 4% by weight of co-monomer perfluoropropyl vinyl ether and having a melt flow rate of 2 g/10 min (3.3 x IO '6 Kg/s) according to ASTM D-21 16.
- PFA perfluoroalkoxy
- the structure thus produced has an elastic modulus of 620 MPa according to ASTM D-790, a total wall thickness of 1 mm, a wall thickness of the PFA layer of 0.5 mm, and a wall thickness of the FEP layer of 0.5 mm.
- the outer diameter of the tube is 12 mm.
- a wide variety of tube diameters and wall thicknesses and ratio's thereof can be produced with the process according to the present invention by using different extrusion heads/toolings and extrusion processing conditions.
- EXAMPLE 2 A flat two-layer structure comprising a PFA layer having a thickness of 2 mm and a FEP layer having a thickness of 1 mm was prepared in essentially the same manner as described in Example 1 with the exception that the extrusion head was different in order to produce a coextruded flat structure with a width of 2 cm (0.02 m).
- a tubular structure (not in accordance with the invention) was produced in a manner similar to that described in Example 1 by extruding polyvinylidene fluoride (PVDF) and ethylene tetrafluoroethylene (ETFE) with a dual-layer extrusion crosshead. The resulting tubular structure was completely delaminated i.e. no adhesion between the PVDF and the ETFE layer was observed.
- PVDF polyvinylidene fluoride
- ETFE ethylene tetrafluoroethylene
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97921464A EP0900140A1 (en) | 1996-04-19 | 1997-04-16 | Multi-layer polymeric structure |
JP09538363A JP2001501551A (en) | 1996-04-19 | 1997-04-16 | Multi-layer polymer structure |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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US1563596P | 1996-04-19 | 1996-04-19 | |
US60/015,635 | 1996-04-19 | ||
US83924697A | 1997-04-15 | 1997-04-15 | |
US08/839,246 | 1997-04-15 |
Publications (1)
Publication Number | Publication Date |
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WO1997039890A1 true WO1997039890A1 (en) | 1997-10-30 |
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ID=26687639
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/007290 WO1997039890A1 (en) | 1996-04-19 | 1997-04-16 | Multi-layer polymeric structure |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0900140A1 (en) |
JP (1) | JP2001501551A (en) |
WO (1) | WO1997039890A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2880011A1 (en) * | 2004-12-23 | 2006-06-30 | Air Liquide Electronics Sys | Chemical product e.g. isopropyl alcohol, distribution system for use in flat screen/light emitting diode fabrication plant, has one tube made of natural polymer such as polyethylene, and perfluoroalkoxy or perfluoroalkoxyl alkane copolymer |
US7141303B2 (en) | 2001-03-06 | 2006-11-28 | 3M Innovative Properties Company | Protective articles |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116888164A (en) | 2021-02-26 | 2023-10-13 | 大金工业株式会社 | Fluorine-containing copolymer |
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US4165404A (en) * | 1975-09-26 | 1979-08-21 | E. I. Du Pont De Nemours And Company | Process for producing laminates of fabric and fluorocarbon copolymer |
EP0171061A2 (en) * | 1984-08-06 | 1986-02-12 | E.I. Du Pont De Nemours And Company | Fluoroelastomer laminates |
WO1988008791A1 (en) * | 1987-05-15 | 1988-11-17 | E.I. Du Pont De Nemours And Company | Dual cured fluoropolymer laminates |
JPH04345836A (en) * | 1991-05-22 | 1992-12-01 | Nitto Denko Corp | Conductive heat-shrinkable tube and its manufacture |
US5320888A (en) * | 1993-11-12 | 1994-06-14 | E. I. Du Pont De Nemours And Company | Fluoroelastomer laminates |
WO1995019883A2 (en) * | 1994-01-24 | 1995-07-27 | Chemfab Corporation | Composites of fluoropolymers with thermally non-adherent non-fluoropolymers and methods for producing the same |
-
1997
- 1997-04-16 WO PCT/US1997/007290 patent/WO1997039890A1/en not_active Application Discontinuation
- 1997-04-16 EP EP97921464A patent/EP0900140A1/en not_active Withdrawn
- 1997-04-16 JP JP09538363A patent/JP2001501551A/en not_active Ceased
Patent Citations (6)
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US4165404A (en) * | 1975-09-26 | 1979-08-21 | E. I. Du Pont De Nemours And Company | Process for producing laminates of fabric and fluorocarbon copolymer |
EP0171061A2 (en) * | 1984-08-06 | 1986-02-12 | E.I. Du Pont De Nemours And Company | Fluoroelastomer laminates |
WO1988008791A1 (en) * | 1987-05-15 | 1988-11-17 | E.I. Du Pont De Nemours And Company | Dual cured fluoropolymer laminates |
JPH04345836A (en) * | 1991-05-22 | 1992-12-01 | Nitto Denko Corp | Conductive heat-shrinkable tube and its manufacture |
US5320888A (en) * | 1993-11-12 | 1994-06-14 | E. I. Du Pont De Nemours And Company | Fluoroelastomer laminates |
WO1995019883A2 (en) * | 1994-01-24 | 1995-07-27 | Chemfab Corporation | Composites of fluoropolymers with thermally non-adherent non-fluoropolymers and methods for producing the same |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7141303B2 (en) | 2001-03-06 | 2006-11-28 | 3M Innovative Properties Company | Protective articles |
US7608323B2 (en) | 2001-03-06 | 2009-10-27 | 3M Innovative Properties Company | Protective articles |
FR2880011A1 (en) * | 2004-12-23 | 2006-06-30 | Air Liquide Electronics Sys | Chemical product e.g. isopropyl alcohol, distribution system for use in flat screen/light emitting diode fabrication plant, has one tube made of natural polymer such as polyethylene, and perfluoroalkoxy or perfluoroalkoxyl alkane copolymer |
WO2006070166A1 (en) * | 2004-12-23 | 2006-07-06 | Air Liquide Electronics Systems | System and method for distributing chemical liquids |
Also Published As
Publication number | Publication date |
---|---|
JP2001501551A (en) | 2001-02-06 |
EP0900140A1 (en) | 1999-03-10 |
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